High metal content complex salts of sulfonic acids and mineral oil compositions thereof



2,739,124 Patented Mar. 20, 1956 HIGH IWETAL CGNTENT COMPLEX SALTS OFULFONIC ACIDS AND MINERAL OIL COM PUSITIGNS Ti-EREOF ApplicationSeptember 4, 1952, Serial No. 307,922

22 Claims. (Cl. 252-33) No Drawing.

This invention relates to improved lubricating oil compositions for usein internal combustion engines. More particularly, it relates to a newclass of detergent additives for such lubricating oils and to a methodfor their preparation.

It is well known that lubricating oils tend to deteriorate under theconditions of use in present day diesel and automotive engines withattendant formation of sludge, lacquer and resinous materials whichadhere to the engine parts, particularly the piston ring grooves andskirts, thereby lowering the operating eficiency of the engine. Tocounteract the formation of these deposits in the engine, certainchemical additives have been found which when added to lubricating oilshave the ability to keep the deposit-forming materials suspended in theoil so that the engine is kept clean and in efficient operatingcondition for extended periods of time. These addition agents are knownin the art as detergents or dispersants. Metal organic compounds areparticularly useful in this respect. These metal organic compounds areconsidered to be effective on the basis of their metal contents coupledwith their solubility in the oil. Generally, it has been found that theoil-soluble metal organic compounds having the greater percentages ofmetal provide the better detergents. On this basis, it has been soughtto provide detergent compounds having the highest possible metalcontents. Metal sulfonates, such as petroleumsulfonates and wax-arylsulfonates, have been found to be particularly eflective detergents formineral lubricating oils. The present invention is concerned with theprovision of a new class of metal sulfonates, hereinafter called complexmetal sulfonates, which have exceptionally high metal contents and whichare highly superior oil detergents. The metal contents of these newcomplex metal detergent salts range from upwards of 50 to about 100 percent higher than the metal contents of normal metal sulfonate salts, i.e., salts havingmetal contents equivalent to the acid-hydrogen contentsof the respective sulfonic acids from which they are derived.

It is, therefore, the object of this invention to provide a new class ofcomplex metal sulfonate salts having exceptionally high metal contents.It is a further object to provide oil compositions containing relativelysmall amounts of these new complex metal salts, which compositions areof high detergent character. Other and further objects will becomeapparent from the following detailed description of the invention.

Broadly, the complex metal salts of this invention are prepared by amethod which comprises (1) intimately contacting an oil, or hydrocarbon,solution of a sulfonic acid, in the presence of water, with (a) at leastabout 1.4 equivalents of a metal hydroxide, (b) at least about 0.3equivalent of a metal chloride and (c) at least about 0.3 equivalent ofa metal carboxylate, said equivalents being based on the equivalents ofacid-hydrogen in the sulfonic acid solution, (2) substantiallycompletely dehydrating the reaction mixture formed in step 1 to producethe complex metal salt product and (3) filtering ofi insoluble material.

A satisfactory procedure for carrying out the invention is as follows:,An aqueous slurry of the three metal-containing reagents is firstprepared. This slurry is then intimately contacted with the sulfonicacid at a temperature of from about 25 C. up to about C. A diluent oilis required in the case of the synthetic type sulfonic acids in order tofacilitate the reaction and the handling and filtration of the complexsalt product. The synthetic sulfonic acids are, therefore, firstdissolved in oil to form a solution of, say, from about 20 to about 60per cent of the acid in the oil, this solution being contacted with thereagent slurry. The petroleum sulfonic acids are, of course, alreadydiluted with oil, generally being pres,- ent therein in amounts of fromabout 20 to about 60 per cent, and these acids, or sour oils, ordinarilyrequire no addition of diluent oil for the purpose of the reaction withthe metal-containing reagents. The contacting of the sulfonic acid(solution) with the reagent slurry is accomplished by slow addition ofthe slurry to the heated acid with constant stirring of the mixture thusformed. When the addition is completed, the mixture is dehydrated byraising the temperature up to about C. and maintaining this temperatureuntil the dehydration is complete. The dehydrated product is thenfiltered to remove excess salt reagent. The product thus obtained is anoil solution which usually contains from about 20 to about 60-75 percent, more or less, of the complex salt. It will be appreciated that inthe case of the synthetic type sulfonic acids other hydrocarbon solventsmay be used for the reaction besides mineral oil, such as a lightnaphtha, xylene, toluene or the like; however, use of a petroleum .oilis preferred since it need not be removed after the reaction, the oilsolution thus obtained being directly blendable with the lubricating oildesired to be fortified with the complex salt product.

Although the aforedescribed procedure is the one generally used, themanner and time of bringing the sulfonic acid solution and the metalcompound reagents together may be varied without afiecting the reaction,or yield of complex salt product obtained. Thus, the sulfonic acidsolution may be added to the reagent slurry, or the sulfonic acid can.be first reacted with themetal hydroxide and then reacted with anaqueous solution of the metal chloride and metal tcarboxylate. Also, thenormal metal sulfonate .may be reacted with a slurry of all threerea'ctants, the slurry containing equivalent amounts of metal hydroxide,metal chloride and metal carboxylate. These and other modifications ofthe procedure of the invention will .be obvious to those skilled in theart. In any case, it is essential to the process of our invention that agood dispersion .of the reactants be obtained, that water be present andthat dehydrationof the reaction mixture be carried to substantialcompletion. As already indicated, it is also necessary that certainminimum amounts of the metal hydroxide, metal chloride and metalcarboxylate reagents be used in the reaction in order to provide thecomplex salts of the invention. The metal chloride and the metal.carboxylate may be supplied in the form of a mixture (slurry) of themetal hydroxide with hydrochloric and carboxylic acids. When the threereagents are supplied in the form of metal salts, at least 1.4equivalents of metal hydroxide, 0.3 equivalent of metal chloride and 0.3equivalent of metal carboxylate are requi'red per equivalent ofacid-hydrogen in the sulfonic acid. However, where the hydrochloric acidand .carboxylic acid are supplied as such to the reaction, the amount ofmetal hydroxide is increased to 2.0 equivalents in. order .to providethe necessary equivalents of metal in he reaction.

The necessity for the presence of water is illustrated by the fact thatwhen dried calcium chloride and calcium acetate, for example, were addedto an oil solution of normal calcium sulfonate and heated, subsequentanalysis of the filtered oil showed no increase in the calcium contentthereof. In general, it may be said than an amount of water equal tofrom about to 50 per cent by weight of the sulfonic acid solutioncharged to the reaction has been found to be satisfactory. The maximumamount of water used is limited only by practical considerations, suchas the amount of reactants used and the time required for dehydration.

The necessity for dehydrating the reaction mixture is illustrated by thefact that if the reaction mixture is not substantially completelydehydrated, but only refluxed for a few hours, the oil phase, whenseparated from the aqueous phase, shows a metal content equal only tothe normal metal sulfonate. The dehydration step has been conductedunder various conditions and there is no definite limitation on themethod of dehydration, except for practical considerations. Generally,the dehydration is accomplished by heating at moderately elevatedtemperatures, i. e., from 50 C. to 120 C., for several hours. Althoughhigher reaction temperatures may be used, they are unnecessary. Thus, inthose instances where the dehydration temperature reached as high as 150C., the metal contents of the products obtained were only slightlyhigher than where the temperature remained below about 100 C. Thedehydration may be facilitated by blowing a gas, such as air ornitrogen, through the heated reaction mixture. Generally, it ispreferable to filter the product at temperatures in the neighborhood of100 C., since this temperature is high enough to keep the product quitefluid.

Due to the intricate nature of the complex metal salts thus produced, nochemical formula can be ascribed to them at this time. Neither is themanner of their formation precisely known. However, without intending tolimit our invention, we believe that our complex salts are formed via atwo-step process in which the normal sulfonate salt is first formed byreaction with the metal hydroxide, the normal salt then being reactedfurther with the metal hydroxide-metal chloride-metal carboxylatereagent during dehydration to yield the final product. The formation ofthe complex salt during dehydration is postulated on the basis ofcertain experimental observations. Thus, although an oil solution ofcomplex metal sulfonate is obtained by interaction of a sulfonic acidwith an aqueous slurry of metal hydroxide, metal chloride and metalacetate by substantially completely dehydrating the reaction mixture (i.e., removal of at least about 90 per cent of the water), if the oilphase is separated-before such dehydration, the metal contentcorresponds only to that of a normal metal sulfonate. Also, indicationsof the formation of complexes between the metal compound reagents duringdehydration are had from X-ray diffraction examination of the solidmaterial obtained on evaporating an aqueous solution of (a) calciumchloride and calcium acetate and (b) calcium hydroxide, calcium chlorideand calcium acetate. Such analyses show no patterns which can beattributed to either calcium chloride or calcium acetate, thusindicating the formation of different compounds. Furthermore, it hasbeen found that more metal can be incorporated into the complex saltproduct by using a mixture of metal chloride and metal acetate alongWith the metal hydroxide than by using an equivalent amount of eithersalt alone. This is believed to be due to the formation of achlorideacetate complex. Finally, since the presence of an appreciateamount of water is necessary in order to form our complex salts,ionization is apparently an essential factor in their formation. 7

We are aware that certain complex metal sulfonate salts have been shownin the prior art. However, the complex salts herein disclosed aredifferent from those heretofore described. Thus, Zimmer et al., No.2,467,176, show the formation of complex metal sulfonate salt detergentsby the reaction of a normal sulfonate salt with either a metal chlorideor a metal acetate and a metal hydroxide. Our

process, however, involves the reaction of three, rather than two,reagent salts with the sulfonic acid, viz., a metal hydroxide, a metalchloride and a metal carboxylate. We have found that by our process muchgreater amounts of metal can be incorporated into the complex salts thanby the method of Zimmer et al. Thus, the highest amount of metal shownby Zimmer et al. is 43 per cent, whereas our complex salts contain fromat least 50 per cent to 90 per cent metal. Our products are, therefore,of a distinct nature from those of Zimmer et al. Furthermore, the mannerof incorporation of excess metal into the sulfonate salts by our methodis apparently different from that of Zimmer et al. This is indicated byanalytical and X-ray diifraction studies of the solids formed uponevaporation of water slurries composed of the reagents used in the twoprocesses. Thus, when a water slurry consisting of calcium chloride andcalcium hydroxide is dehydrated (Zimmer et al.), the analytical andX-ray data indicate the formation of a calcium hydroxide-calciumchloride complex, whereas in the case of a Water slurry containingcalcium hydroxide, calcium chloride and calcium acetate, it is foundthat the solid consists predominantly of a calcium chloride-calciumacetate cornplex along with a minor amount of a calcium hydroxidecalciumchloride-calcium acetate triple component complex, without any calciumchloride-calcium hydroxide complex being present.

In the grease art, several patents, viz., Zimmer et al., No. 2,444,790,and OHalloran, Nos. 2,553,422 and 2,563,814, disclose complex sulfonatesalts as gelling agents. These salts are formed by reaction of normalsulfonate salts with low molecular weight acid salts, such as metalcarboxylates. Our complex salts, however, are distinguished from thecomplex salts of these patents by virtue of the fact that these lattersalts are oil-insoluble and provide grease-like structures in the oil,whereas our complex salts are oil-soluble. Since the composition of ourcomplex salts is different from that of the complex salts of the priorart, they are claimed herein as new compositions of matter.

I The metal constituents of the metal hydroxide, metal chloride andmetal carboxylate reactants used in the prepprepared and tested complexsalts containing two and three metal constituents and have found them tobe highly effective detergents as shown in the examples presentedhereinafter. Up to the present time, our Work has extended only tothemetal salts of those metals falling within group I and group II of theperiodic table. However, it seems probable that reagent salts of othermetals will also be found to be suitable for the invention. We havefound that the alkaline earth complex metal salts, particularly thecalcium salts and the mixed calciumbarium salts, provide outstandingdetergents for lubricating oils.

The carboxylic acids, or salts thereof, suitable for the preparation ofour complex metal salts are the aliphatic monocarboxylic acids havingfrom 1 up to about 20 carbon atoms in the aliphatic portion thereof. Theacid used may be either saturated or unsaturated. it may also containcertain substituent groups, such as phenyl, hydroxy, halogen, amino ormercapto groups. As noulimiting examples of such acids there may bementioned formic acid, acetic acid, chloroacetic acid, phenyl'aceticacid, hydroxy acetic acid, glycine, thioglycollic acid, acrylic acid,propionic acid, butyric acid, butenic acid, valeric acid, heptylic acid,caproic acid, lauric acid, myristic acid, palmitic acid, oleic acid,stearic acid and the like. The lower molecular weight acids, such asformic and acetic acids, are preferred however, since they providecomplex salts having the higher proportions of metal per mol of complexsalt.

As aforesaid, the sulfonic acids suitable for use in this inventioninclude oil-soluble petroleum sulfonic acids and synthetic alkarylsulfonic acids. The sulfonic acids having higher molecular weights, i.e., from about 300 to about 800, are particularly preferred. Thesesulfonic acids may be produced by sulfonation of petroleum stocks orsynthetic alkyl aromatic compounds, such as alkyl-substituted benzenesor naphthalenes, wherein the alkyl groups attached to the aromatic ringcontain at least about 8 carbon atoms, the wax-substituted benzenes andnaphthalenes being particularly preferred. The petroleum sulfonic acids,also known as sour oils, are those obtained in the treatment ofpetroleum oils, particularly refined, or semi-refined oils, withconcentrated or fuming sulfuric acid, and which remain in the oil aftersettling out of sludge. These sulfonic acids may be represented by thegeneral formula (1K)" SOJH where R is one or more alkyl, alkaryl oraralkyl groups and the aromatic nucleus is a single or condensed ring orpartially hydrogenated ring. Example 1 illustrates the preparation of atypical petroleum sulfonic acid. The oil used was a furfural-refined,Mid-Continent heavy distil- Preparation of petroleum sulfonic acid Thecharge oil was treated with 30 per cent by weight of 103 to 104 per centsulfuric acid by adding the acid gradually to the oil over a period ofabout 2 hours, the mixture being agitated by airblowing and thetemperature being maintained at 100 to 120 F. during the addition.Following this, the product was treated with quench water (about 6 percent by weight of charge oil) in order to dilute the sulfuric acid andfacilitate separation of acid and sludge from the sulfonic acid (souroil). The water was added over a period of about -30 minutes, so thatthe temperature of the mixture was maintained at 115160 F. The crudesour oil was allowed to settle for about 18 hours, after which sludgeand spent acid were withdrawn and the product blown with air at about160 F. to remove occluded S02. This was followed by a final settlingperiod of 50 hours at 160 F. to insure as complete removal as possibleof spent acid and sludge. The yield of sour oil was approximately 97 percent by weight of the oil charged. The total N. N. (neutralizationnumber) of the product was 24.1 and the true N. N. 19.6. The total N. N.designates the combined acidity of the sulfonic acid and residualsulfuric acid in the sour oil while the true N. N. designates theacidity due to the sulfonic acid content of the sour oil alone.

Preparation of calcium chloride-acetate-sulfonate complex The sulfonicacid, prepared as above described, was

utilized to prepare a calcium chloride-acetate-sulfonate complex salt,as set forth in the following example.

EXAMPLE 2 Materials: I

400 grams of sour oil (Total N. N.=24.1, True N. N.=19.6) 3.2 grams ofacetic acid (glacial) (0.3 equivalents based on total N. N. of sour oil)3.8 grams of Dowfiake (77 per cent CaClz, 0.3

equivalents based on total N. N. of sour oil) 11.1 grams of greasemakers lime (96 per cent Ca(OH)z, 1.68 equivalents) 100 cc. of H20 20grams of Hyflo filter-aid Procedure.The calcium reagent was made byadding the acetic acid to a slurry prepared by dissolving the calciumchloride in a portion of the water and adding this solution to a slurryof the lime in the major portion of the water. It is advisable to retainabout 20 cc. of water for washing to insure essentially completetransfer of the reagents from the vessel to the reaction mixture. Thesour oil was placed in a l-liter, four-necked, round-bottorned ilaskequipped with a mechanical stirrer, thermometer, air inlet tube, and aDean-Stark water takeoff fitted with a reflux condenser. The sour oilwas heated with stirring and with a moderate stream of air passingthrough it to approximately 75 C. The reagent slurry was then addedslowly to the sour oil over a one-hour period from a dropping funnel.The slurry was stirred from time to time to assure homogeneity. When theaddition was complete, more heat was applied and the water removed bymeans of the Dean-Stark take-off. The removal of the water took about 1/2 hours with the temperature regulated so as not to exceed about 100 C.To insure dryness, dehydration was continued for another hour after thecontents of the reaction vessel appeared bright and dry. Twelve grams ofHyfio (a diatomaceous earth filter-aid) were stirred into the productwhich was then filtered through a filter paper packed with Hyflo in aheated Biichner funnel. Three hundred seventyfive grams of product, abrownish-red oil, was obtained.

Analysis of product:

Percent calcium=1.25 (79 per cent in excess of a normal salt) Percentsulfur=l.27 Percent chlorine=0.16 K. V. 210, F.=21.l4 Potentiometricbase No.=12.0

EXAMPLES 3-l2 As stated hereinbefore, we have found that the use ofabout 1.4 equivalents of metal hydroxide, about 0.3 equivalent ofcalcium chloride and about 0.3 equivalent of calcium carboxylate providethe best results in the preparation of our complex metal salts, theseamounts being based on the acid-hydrogen value of the crude sulfonicacid (i. e., the total N. N.). It is to be understood, however, thatthese proportions may vary somewhat depending upon the residual sulfuricacid content of the particular sour oil or synthetic sulfonic acid used.This sulfuric acid content may vary in amount from about several percent to 20-30 per cent of the total acid content in different sour oilsand for the obtainment of optimum results the metal chloride and acetatereagents can be varied proportionately, i. e., they may be decreasedwith an increase in the sulfuric acid value and vice versa. Examples4-12 illustrate the effect of varying the amounts of calcium hydroxide,calcium chloride and calcium acetate used on the metal contents of thecomplex salt products. The sulfonic acid utilized in these examples wasthat prepared in Example 1 and the method of preparing the complex saltswas that of Example 2. The results are summarized in Table I.

8 an increase in, the amount of the magnesium acetate reagent up to 0.9equivalent providesa complex salt product having exceptionally highmetal. content. Also, as aforesaid, some variation in the amount ofmetal salt reagent must be permitted depending upon the residualsulfuric acid content of the particular sulfonic acid utilized. Theamounts of the reagent salts designated herein, therefore, actuallyrepresent about the least amounts which TABLE I.-PREPARATION F COMPLEXCHLORIDE-ACETATE-CALClIiM summers Reagents Employed For 4%0 (1111231111Sglignc Ae1d--Tota1 N. N.=24.1; Analysis of Product Example Number LimeC201: 3 OHaCQOH Ca(OAc)z ce t Potentm Perceent Excess P81861113 T meltgePerzent Equiv- Equiv- Equiv- Equiv- C8 1 a 358 Grams alents Grams alentsG1 ems a1 ems Grams alems No.

9. 8 1. 2. 5 0. 2 2. 1 0. 2 0. 99 41 0. 24 6. 7 1. 19 11.1 1. 7 3. 8 0.3 3. 2 0. 3 1.25 79 0.16 12.0 1. 27 4 33. 3 1. 7 11. 4 0. 3 9.6 0. 3 1.24 79 0.15 12.0 1. 29 12.5 1. Q 5. 0 0. 4 4. 2 0.4 1. 86 0. 19 12. 0 13.2 2. 0 3. 8 0. 3 3. 2 0. 3 1. 3O 86 0. 14 11. O 1. 14. 5 2. 20 3. 8 0. 33. 2 0. 3 1. 35 93 0. 16 12.0 1.31 11.1 1. 7 3.8 0. 3 6. 4 0. 6 0.87 240. 2 5. 5 1.05 11. 1 1. 7 7. 6 O. 6 3. 2 0. 3 1. 16 0. 12 9. 1 1. 30 13.3 2.0 2. 5 0.2 10. 3 1. 0 0. 63 13. 3 2.0 12. 5 1.0 10. 3 1.0 0.72 1. 04

1 Per equivalent of sultonie acid, based on total N. N.

1 Normal salt would have 0.7% Ca, based on true N. N. Dowflake 77%.

4 1,200 grams of sulfonic acid used in this example.

In Examples 4 and 5, the preferred amounts of reagents were used. Itwill be seen that where the amounts of the reagents were decreased to1.3 equivalents of calcium hydroxide, 0.2equivalent of calcium chlorideand 0.2 equivalent of calcium acetate per equivalent of acid-hydrogen inthe sour oil, the calcium content of the product was decreased (Example3). On the other hand where the amounts of the reagents are increased to1.5 equivalents of calcium hydroxide, 0.4 equivalent of calcium chlorideand 0.4 equivalent of calcium acetate per equivalent of acid-hydrogen inthe sour oil, a slight increase in calcium content of the product wasachieved (Example 6). However, the increase is not. in proportion to theincrease in calcium content of the reagent; and, difiiculties infiltration were encountered due to the excessive amounts of reagentsemployed. Again, where the calcium chloride and calcium acetate werekept constant at 0.3 equivalent and the calcium hydroxide content of thereagent slurry was increased to 1.9 (Example 7) or even 2.2 equivalents(Example 8) a slight increase in calcium content was achieved, but,again, filtration difficulties were encountered. If the calciumhydroxide and calcium acetate are held constant at the preferred ratioand the calcium chloride is increased to 0.6 equivalent, the calciumcontent of the product is decreased (Example 10). Increasing the calciumacetate content of the slurry in a significant amount above thepreferred ratio resulted in a decrease in calcium content of the finalproduct, even when the calcium hydroxide and calcium chloride werevaried over wide limits (Examples 9, 11 and 12). This is believed to bedue to the formation of complexes similar to those described in thegrease art which are insoluble in oil and are removed during filtration.Generally, the preferred proportions found for the calcium reagents arealso applicable to the reagent salts of the other metals contemplatedherein, although some variation from these proportions in certaininstances and in the case of certain metals provide products of highermetal content. Such variations in the amounts of reagent salts used are,therefore, within the scope of our invention. For example, where themetal constituent of the reagent salts is magnesium may be utilized forthe successful preparation of the complex salt products having the highmetal contents contemplated herein, but are not the exact amounts to beused in any and all cases.

A typical synthetic wax-aryl sulfonic acid, viz., waxbenzene (2-12)sulfonic acid was prepared as shown in the following example.

EXAMPLE 13 Preparation of wax-benzene (2-12) sulfonic acid A parafiinwax having an average of 24 carbon atoms per molecule and a meltingpoint of 126 F. was chlorinatcd at a temperature of about 100 C. withchlorine gas until the weight of the wax had increased about 12 percent. The chlorowax thus obtained was then blown with nitrogen to removeany occluded chlorine and hydrogen chlorine.

One thousand grams of the chlorowax were then mixed with 500 grams ofbenzene in a 3-neclced flask equipped with a stirrer, a reflux condenserand a thermometer. The mixture was heated to a temperature of 60 C.Aluminum chloride was then added slowly over a period of two hours. Theaddition of aluminum chloride was accompanied by a vigorous evolution ofhydrogen chloride. The temperature was then raised to a temperature ofC. and held there for one 'hour. The excess benzene was then removed byinverting the reflux condenser and heating to a temperature of 116 C.Two hundred milliliters of benzene were thus recovered. The mixture wascooled to a temperature of 60 C. and then another 1000 grams ofchlorowax were added slowly. After completing the addition of thischlorowax, the temperature was raised to C. and held there for one hour.The product was allowed to stand overnight at a temperature of about 60C., and then was separated from the sludge by decantation and filtrationby suction through clay.

One thousand seven hundred and thirty-eight grams of the wax-benzenethus obtained were placed in a 3-necked flask equipped with a stirrerand a thermometer and heated to a temperature of 40 C. Eight hundredsixty-nine grams of oleum (15 per cent S03) were addedslowly to thewax-benzene from a dropping funnel at a rate regulated to maintain thetemperature below 50 C. The addition of oleum consumed about 3 hours.The mixture was then stirred for an additional hour to ensure completereaction. The mixture was then poured into 1000 milliliters of water andsubsequently, 1810 grams. of mineral oil were added to the mixture. Themixture thus obtained was stirred thoroughly and then allowed to standuntil the water separated into a layer. The water layer was then drained01f. The product thus obtained was approximately a 50 per cent blend ofwax-benzene sulfonic acid in mineral oil and had a neutralization numberof 40.7.

It will be understood that a, wax-benzene prepared according to theforegoing procedure in which a quantity of chlorowax containing 2 atomicproportions of chloride and having a chlorine content of 12 per cent isreacted with 1 mole of benzene is designated wax-benzene (212).Similarly, wax-benzene (340) and waxbenzene (1-10) may be also preparedby the reaction of sufiicient amounts of chlorinated wax, containing1-0. per cent by weight of chlorine, to provide 3 atomic proportions and1 atomic proportion of chlorine per mole of benzene, respectively, inthe reaction are useful in the invention. In general, the amount ofchlorowax containing from about 10 to about 18 per cent by weight ofchlorine used in the reaction is suflicient to supply between 1 and 4atomic proportions of chlorine per mole of benzene used.

Two complex salts of wax-benzene (2-12) sulfonic acid, prepared asdescribed in the above-example, were prepared, viz., (1) a complexacetate-chlorid'e-calcium sulfonate (Example 14) and (2) a complexacetate-chloridemagnesium sulfonate (Example 15).

TABLE II.PREPARATION F COMPLEX CALCIUM 1.8.6. grain grease.v makers?little 6% per cent Ca(OH)2, 1.68 equivalents) 170 cc. H2O

Procedure.-The calcium reagent was made by adding the acetic acid to aslurry prepared by dissolving the cal- The wax-benzene sulfonic acid washeated with stirring.

and with a moderate stream of nitrogen passing through it toapproximately 75 C. The calcium reagent was then added slowly to thewax-benzene; sulfonic acid. over a one-hour period from a droppingfunnel. When the addition was complete, more heat was applied and thewater was removed by means of the Dean-Stark take-off. The reactionmixture was gradually heated to about 105 C. and, to ensure completedehydration, held at this temperature for a period of about one hour.

Twelve grams of Hyflo filter aid were stirred into the product mixturewhich was then filtered through a Hyfio packed filter paper in a heatedBiichner funnel. The product was a viscous brown oil.

EXAMPLE 15 Preparation of complex acetate-chloride magnesium waxbenzene(2-12) suljfonate This salt was prepared by a procedure identical tothat used in Example 14, except that magnesium hydroxide, magnesiumchloride and, magnesium acetate salt reagents were utilized in place ofthe corresponding calcium salts.

The details. relative to Examples 14 and 15 are given in Table II.

SALTS OF WAX-BENZENE (2-12) SULFONIO ACID Reagents 1 fggff DiluentExample Sammie Process Hydroxide Component Chloride Component Number #5Oil,

3 5, Grams 4 Formula Grams gg Formula Grams gi g 14 40,0 Ca(OH); 18.6 1.7 0.11011 6.4 0.3 15. 400 150 Mg( OH) 1 21. 7 2. 3 MgQl1.6Hz0 10. 4' 0.3.

Reagents 1 Analysis of Product llIxamlple Carboxylate Component P um 81'ercent Total Base fizg Excess g Percent No. Poten- Formula Grams gg?Metal tiometrlc 14 CHQOOOH 5. 4 0. 3 2.14 Ga. 2 54 0. 56 2. 15 14 15.--CHQOOOH 17. 6 0.9 1.63 Mg 87 0. 19 1. 87 29 3 Normal calcium sulfonatewould have 1.39%

Ga based on true N. N. (39.5).

= This material contains about diluent oil. 4 A conventionally refinedMid-Continent (parafiinic) neutral distillate oil having a K. V. of 100sec. at 100 F.

EXAMPLE 14 Preparation of complex acetate-chloride calcium waxbenzene(212) sulfonaie Materials EXAMPLES 16-28 A number of complex salts ofpetroleum sulfonic acids were prepared using salt reagents of metalsother than calcium (Examples 16-20). A number of mixed metal 400 gramswax-benzene 2-12) sulfonic. acid (total calcium salts were also prepared(Examples 21-25). The

5.4 grams acetic acid (glacial) (0.3 equivalent based total N. N.)

6.4 grams dowtlake (77 per cent CaCIz, 0.3 equiv alent based on total N.N.)-

procedure used was that of Example 2. In several of these examples,aliphatic acids other than acetic acid were used, such as formic acid(Example 28), propionic acid (Example 26) and heptylic acid (Example27). Details. as to these examples are given in Table HI.

TABLE [11.-METAL AND MIXED METAL COMPLEX SALTS OF PETROLEUM BULFONIOAGID Reagents Employed For 400 Grams Sulfonio Acid-Total N N=24.1; TrueNN=19.6

Example Hydroxide Component Chloride Component Carboxylate Number ponentFormula fig Grams Formula ggg Grams Formula 16 Mg(OH): 1. 7 8. 5MgClz.6H20 0. 3 5. 3 CHaCOOH 17 Mg(OH)2 2. 10. 0 MgClafiEzO 0. 3 5. 30131000011 18 Mg(OH)2 2. 3 11. MgC1z.6H2O 0. 3 5. 3 CHaCOOH 19Ba(OH)28HzO 1. 7 46 1321012213120 0. 6 12. G CHaCOOH 20 NaOH 1. 7 12. 1NaCl 0. 3 3. 02 GHBOOOH 21 08(OH): 1. 7 11. 1 MgClziiHzO 0. 3 5. 3CHSOOOH 22 0&(0H): 1. 7 11. 1 ZnCl: 0. 3 3. 7 H300 23 Mg(OH)z 1. 4 7. 3Z1101: 0. 3 3. 7 Ca(C2HaO2)2 H 24 Ba.(OH)z.8H2O 1. 4 38 021012 0. 3 3. 809.201102. 2 25 Mg(0H)l 1. 4 7.0 021012 0. 3 3. 8 Ca OAc)z.HzO 26Ca(OH): 1. 7 11. 1 08.012 0. 3 3. 8 CHaCHzCOOH 27 Ca(OH): 1. 7 11. 109.012 0. 3 3. 8 CH3(CH2)5COOH 28 Ca(OH): 1. 7 11. 1 OaCl: 0. 3 3. 8HCOOH Reagents Enplloyed FXrOO rams u omo c1 Total NN=24.1; Tru AnalysisOf Product NN=19.6

Example Number 0 b 1 t C t at oxy a e omponen Total Total PercentMei-5a1 Metal Percent Percent Base N o. E uiva- Water 1103? Equiva 111251 1 0 Potent" fl Grams cc lents ornetrrc 0. 3 3. 1 100 0.79 (Mg).. 1.89 89 0. 22 9. 7 0. 6 6. 2 100 0.94 (Mg) 2. 23 2. 23 123 0. 26 17 0. 99. 3 100 1.07 (Mg) 2. 6 2. 6 160 0. 31 0. 3 3. 2 100 4.6 (Ba)--- 2. 0100 07 7. 1 0. 3 3. 1 100 1.30 (Na) 1. 63 1. 63 63 0. 11 11. 4 0. 3 3. 1100 1.00 (0a)-- 1. 41 1. 57 57 0. 19 4. 3

0.07 (Mg) 16 0. 3 3. 1 150 1.14 (0a).- 1. 6 1. 85 85 0. 18 13 0.3 (Zn)254 0. 3 4. 6 150 0.14 (C3)" 0. 2 1. 63 63 0. 29 6. 5

0.54 (Mg) 1. 27 0.18 (Zn 156 0. 3 4. 6 160 0.20 (C 0. 29 1. 77 77 0. 237. 1

0.42 (Mg) 1. 00 0. 3 3. S 100 1.23 (Ga) 1- 1. 77 1. 77 77 0. 18 11 0. 36. 7 100 1.23 (0a)-. 1. 77 1. 77 77 0. 10 11 0. 3 2. 4 100 1.14(0a)-- 1. 63 1. 63 63 0. 14 10 Engine evaluation parative purposes, theresults obtained with the blank oil T 0 demonstrate the ability of thecomplex chlorideare also Included. The 011 used these. tests was an e b1a t at 1 U1 f0 ate u of the invention as SAE grade, acid-refinedcoastal o1l havlng a K. V. at M e m a s S 100 F. of 132.7 and at 210 F.of 9.82. Both the blank lubricating oil detergents, We have prepared oilblends of a. number of such salts and tested these oil blends in the CFRdiesel D-2l detergency test. Table IV shows the tabulated results forthe various oil blends. For comoil and the oil blends contained 1.0% ofantioxidant (pinene-PzSa product). These test data show the highefficiency of the complex salts of the invention as detergents in engineoils.

TABLE IV.-OFR COMET DIESEL TEST (D-21) (HIGH SULFUR FUEL-SAE 30 BASEOIL) Product 01' Example No.

Piston Cleanliness Rating At Hours Sulfonate Type Percent Composition OfReagent Additive Petroleum.

Diesel (D-21') detergency test This test determines the effectiveness ofthe lubricating oil in preventing piston deposits and top ring wear.

A single cylinder CFR, 4-cycle, super-charged, diesel engine is used.The operating conditions are as follows:

Oil temperature F 175 Jacket temperature F" 212 Speed R. P. M 1800 Brakeload H. P 7.5 Oil addition every 8 hours starting at 4 hours (1 /2 gal.sample used) Heat input B. t. u./min. 1260 The duration of the test is60 hours. The fuel used is a N0. 2 fuel oil containing 1 per centsulfur. The results are reported in terms of piston cleanliness ratings.

Various grades of lime, such as grease makers lime, Bell-Mine chemicalgrade hydrated lime and chemically pure lime, may be used in preparingthe complex calcium salts of this invention. However, grease makers limeis preferred because of its high purity, small particle size and itsproperty of being wet by oil.

The amount of complex salt product utilized in a lubricating oil willdepend upon the particular oil and the application for which it isdesigned. Generally, amounts ranging from about 0.1 up to about 20weight per cent may be used, the usual amount being from about 0.5 toabout 10 weight per cent.

The complex salt products of this invention may be used in lubricatingoil compositions containing other addition agents designed to improvethe oil in different respects, e. g., antioxidants, extreme pressureagents, pour point depressants, viscosity index improvers, defoamants,etc.

Although the complex salts of this invention are intended primarily foruse as lubricating oil additives, they are also adaptable for use inother applications, e. g., they find application in the manufacture ofdetergent soaps and are useful as dispersants and rust reventives. Theymay also be used as additives for cutting and textile oils.

Although the preparation and utility of certain specific representativecomplex salt products, and oil compositions thereof have been describedin detail herein, it is not intended that the invention be limited inany Way thereby, but that it include such variations and procedures andsuch products and compositions as come within the spirit and scope ofthe accompanying claims.

We claim:

1. A complex metal salt of a hydrocarbon-soluble sulfonic acid producedby the method which comprises the steps of: (l) forming a mixture of ahydrocarbon solution of the sulfonic acid with water and a reagentcombination which will provide in said mixture at least about 1.4equivalents of metal hydroxide, at least about 0.3 equivalent of metalchloride and at least about 0.3 equivalent of an aliphatic metalcarboxylate having from 1 to about 20 carbon atoms in the aliphaticportion thereof; the equivalents of said metal hydroxide, metal chlorideand metal carboxylate being based on the total equivalents ofacid-hydrogen present in the hydrocarbon solution of the sulfonic acidand the metal constituent of said metal hydroxide, metal chloride andmetal carboxylate being a metal selected from groups I and ii of theperiodic table of the elements, (2) substantially completely dehydratingthe reaction mixture formed in step 1 and (3) filtering oii insolublematerial.

2. A complex metal salt of a petroleum sulfonic acid produced by themethod which comprises the steps of (l) intimately contacting an oilsolution of the sulfonic acid, in the presence of water, with at leastabout 1.7 equivalents of calcium hydroxide, at least about 0.3equivalent of calcium chloride and at least about 0.3 equivalent ofacetic acid, the equivalents of said calcium hydroxide, calcium chlorideand acetic acid used being 14 based on the total equivalents ofacidrhydrogenipreseut in. said oil solution of the sulfonic acid, (2)substantially completely dehydrating the reaction mixture formed in step1 and (3) filtering off insoluble material.

3. A complex metal salt of an oil-soluble synthetic wax-benzene sulfonicacid produced by the method which comprises the steps of (l) intimatelycontacting an oil solution of the wax-benzene sulfonic acid, in thepresence of water, with at least about 1.7 equivalents of calciumhydroxide, at least about 0.3 equivalent of calcium chloride and atleast about 0.3 equivalent of acetic acid, the equivalents of saidcalcium hydroxide, calcium chloride and acetic acid used being based onthe total equivalents of acid-hydrogen present in said oil solution ofthe sulfonic acid, (2) substantially completely dehydrating the reactionmixture formed in step 1 and (3) filtering ofi insoluble material.

4. A complex metal salt of a petroleum sulfonic acid produced by themethod which comprises the steps of (l) intimately contacting an oilsolution of the sulfonic acid, in the presence of water, with at, leastabout 1.7 equivalents of calcium hydroxide, at least about 0.3equivalent of calcium chloride and at least about 0.3 equivalent offormic acid, the equivalents of said calcium hydroxide,

calcium chloride and formic acid used being based onthe totalequivalents of acid-hydrogen present in said oil solution of thesulfonic acid, (2) substantially comp-letely dehydrating the reactionmixture formed instep and (3) filtering oft" insoluble material.

5. A complex metal salt of a petroleum sulfonic acid produced by themethod which comprises the steps of (l) intimately contacting an oilsolution of the sulfonic acid, in the presence of water, with at leastabout 1.7 equivalents of magnesium hydroxide, at least about, 0.3equivalent of magnesium chloride and at least about 0235 equivalent ofacetic acid, the equivalents of said mag nesium hydroxide, magnesiumchloride and acetic acid used being based on the total equivalents ofacid-hydrogen present in said oil solution of the sulfonic acid, (2)substantially completely dehydrating the reaction mixture formed, instep 1 and (3) filtering off insoluble material.

6. A complex metal salt of a petroleum sulfonic acid produced by themethod which comprises the steps of (l) intimately contacting an oilsolution of the sulfonic acid, in the presence or" water, with at leastabout 1.7 equivalents of barium hydroxide, at least about 0.3 equivalent of barium chloride and at least about 0.3 equivalent of aceticacid, the equivalents of said barium hydroxide, barium chloride andacetic acid used being based on the total equivalents of acid-hydrogenpresent in said oil solution of the sulfonic acid, (2) substantiallycompletely dehydrating the reaction mixture formed in step 1 and (3)filtering oil insoluble material.

7. A complex metal salt of a petroleum sulfonic acid produced by themethod which comprises the steps of (1) intimately contacting an oilsolution of the sulfonic acid with an aqueous reagent slurry containingat least about 1.7 equivalents of calcium hydroxide, at least about 0.3equivalent of calcium chloride and at least about 0.3 equivalent ofacetic acid, the equivalents of said calcium hydroxide, calcium chlorideand acetic acid used being based on the total equivalents ofacid-hydrogen present in said oil solution of the sulfonic acid, (2)substantially completely dehydrating the reaction mixture formed in step1 and (3) filtering of? insoluble material.

8. A complex metal salt of an oil-soluble synthetic wax-benzene sulfonicacid produced by the method which comprises the steps of (l) intimatelycontacting an oil solution of the wax-benzenesulfonic acid with anaqueous reagent slurry containing at least about 1.7 equivalents ofcalcium hydroxide, at least about 0.3 equivalent of calcium chloride andat least about 0.3 equivalent of acetic acid, the equivalents of saidcalcium hydroxide, calcium' chloride and acetic acid used being based onthe total equivalents of acid-hydrogen present in said oil solution ofthe sulfonic acid, (2) substantially completely dehydrating the reactionmixture formed in step 1 and (3) filtering otf insoluble material.

9. A complex metal salt of a petroleum sulfonic acid produced by themethod which comprises the steps of (1) intimately contacting an oilsolution of the sulfonic acid with an aqueous reagent slurry containingat least about 1.7 equivalents of calcium hydroxide, at least about 0.3'equivalent of calcium chloride and at least about 0.3 equivalent offormic acid, the equivalents of said calcium hydroxide, calcium chlorideand formic acid used being based on the total equivalents ofacid-hydrogen present in said oil solution of the sulfonic acid, (2)substantially completely dehydrating the reaction mixture formed in step1 and (3) filtering off insoluble material.

10. A complex metal salt of a petroleum sulfonic acid produced by themethod which comprises the steps of (1) intimately contacting an oilsolution of the sulfonic acid with an aqueous reagent slurry containingat least about 1.7 equivalents of magnesium hydroxide, at least about0.3 equivalent of magnesium chloride and at least about 0.3 equivalentof acetic acid, the equivalents of said magnesium hydroxide, magnesiumchloride and acetic acid used being based on the total equivalents ofacidhydrogen present in said oil solution of the sulfonic acid, (2)substantially completely dehydrating the reaction mixture formed in step1 and (3) filtering off insoluble material.

11. A complex metal salt of a petroleum sulfonic acid produced by themethod which comprises the steps of (1) intimately contacting an oilsolution of the sulfonic acid with an aqueous reagent slurry containingat least about 1.7 equivalents of barium hydroxide, at least about 0.3equivalent of barium chloride and at least about 0.3 equivalent ofacetic acid, the equivalents of said barium hydroxide, barium chlorideand acetic acid used being based on the total equivalents ofacid-hydrogen present in said oil solution of the sulfonic acid, (2)substantially completely dehydrating the reaction mixture formed in step1 and (3) filtering off insoluble material.

12. A mineral lubricating oil containing a minor proportion, sutficientto improve the detergent ability of said oil, of a complex metal salt ofa hydrocarbonsoluble sulfonic acid produced by the method whichcomprises the steps of: (1) forming a mixture of a hydrocarbon solutionof the sulfonic acid with water and a reagent combination which willprovide in said mixture at least about 1.4 equivalents of metalhydroxide, at least about 0.3 equivalent of metal chloride and at leastabout 0.3 equivalent of an aliphatic metal carboxylate having from 1 toabout 20 carbon atoms in the aliphatic portion thereof, the equivalentsof said metal hydroxide, metal chloride and metal carboxylate beingbased on the total equivalents of acid-hydrogen present in thehydrocarbon solution of the sulfonic acid and the metal constituent ofsaid metal hydroxide, metal chloride and metal carboxylate being a metalselected from groups I and II of the periodic table of the elements, (2)substantially completely dehydrating the reaction mixture formed in step1 and (3) filtering off insoluble material.

13. A mineral lubricating oil containing a minor proportion, sufiicientto improve the detergent ability of said oil, of a complex metal salt ofa petroleum sulfonic acid produced by the method which comprises thesteps of. (1) intimately contacting an oil solution of the sultonicacid, in the presence of Water, with at least about 1.7 equivalents ofcalcium hydroxide, at least about 0.3 equivalent of calcium chloride andat least about 0.3 equivalent of acetic acid, the equivalents of saidcalcium hydroxide, calcium chloride and acetic acid. used being based onthe total equivalents of acid-hydrogen present in said oil solution ofthe sulfonic acid, (2) substantially completely dehydrating the reactionmixture formed in step 1 and (3) filtering off insoluble material.

14. A rnineral lubricating oil containing a minor pro- Cir ' step 1portion, sulficient to improve the detergent ability of said oil, of acomplex metal salt of an oil-soluble synthetic wax-benzene sulfonic acidproduced by the method which comprises the steps of (1) intimatelycontacting an oil solution of the wax-benzene sulfonic acid, in thepresence of water, with at least about 1.7 equivalents of calciumhydroxide, at least about 0.3 equivalent of calcium chloride and atleast about 0.3 equivalent of acetic acid, the equivalents of saidcalcium hydroxide, calcium chloride and acetic acid used being based onthe total equivalents of acid-hydrogen present in said oil solution ofthe sulfonic acid, (2) substantially completely dehydrating the reactionmixture formed in step 1 and (3) filtering off insoluble material.

15. A mineral lubricating oil containing a minor proportion, sufiicientto improve the detergent ability of said oil, of a complex metal salt ofa petroleum sulfonic acid produced by the method which comprises thesteps of (1) intimately contacting an oil solution of the sulfonic acid,in the presence of water, with at least about 1.7 equivalents of calciumhydroxide, at least about 0.3 equivalent of calcium chloride and atleast about 0.3 equivalent of formic acid, the equivalents of saidcalcium hydroxide, calcium chloride and formic acid used being based onthe total equivalents of acid-hydrogen present in said oil solution ofthe sulfonic acid, (2) substantially completely dehydrating the reactionmixture formed in step 1 and (3) filtering otf insoluble material.

16. A mineral lubricating oil containing a minor proportion, suflicientto improve the detergent ability of said oil, of a complex metal salt ofa petroleum sulfonic acid produced by the method which comprises thesteps of (1) intimately contacting an oil solution of the sulfonic acid,in the presence of water, with at least about 1.7 equivalents ofmagnesium hydroxide, at least about 0.3 equivalent of magnesium chlorideand at least about 0.3

equivalent of acetic acid, the equivalents of said magne-, siumhydroxide, magnesium chloride and acetic acid portion, sufficient toimprove the detergent ability of said oil, of a complex metal salt of apetroleum sulfonic acid produced by the method which comprises the stepsof (1) intimately contacting an oil solution of the sulfonic acid, inthe presence of water, with at least about 1.7 equivalents of bariumhydroxide, at least about 0.3 equivalent of barium chloride and at leastabout 0.3

equivalent of acetic acid, the equivalents of said barium hydroxide,barium chloride and acetic acid used being based on thetotal equivalentsof acid-hydrogen present in said oil solution of the sulfonic acid, (2)substantially completely dehydrating the reaction mixture formed in step1 and (3) filtering oft insoluble material.

18. A mineral lubricating oil containing a minor proportion, sufiicientto improve the detergent ability of said oil, of a complex metal salt ofa petroleum sulfonic acid produced by the method which comprises thesteps of (1) intimately contacting an oil solution of the sulfonic acidwith an aqueous reagent slurry containing at least about 1.7 equivalentsof calcium hydroxide, at least about 0.3 equivalent of calcium chlorideand at least about 0.3

equivalent of acetic acid, the equivalents of said calcium hydroxide,calcium chloride and acetic acid used being based on the totalequivalents of acid-hydrogen present in said oil solution of thesulfonic acid, (2) substantially completely dehydrating the reactionmixture formed in and (3) filtering oil insoluble material.

19. A mineral lubricating oil containing a minor proportion, suflicientto improve the detergent ability of said oil, of a complex metal salt ofan oil-soluble synthetic Wax-benzene sulfonic acid produced by themethod which comprises the steps of (1) intimately contacting an oilsolution of the wax-benzene sulfonic acid with an aqueous reagent slurrycontaining at least about 1.7 equivalents of calcium hydroxide, at leastabout 0.3 equivalent of calcium chloride and at least about 0.3equivalent of acetic acid, the equivalents of said calcium hydroxide,calcium chloride and acetic acid used being based on the totalequivalents of acid-hydrogen present in said oil solution of thesulfonic acid, (2) substantially completely dehydrating the reactionmixture formed in step 1 and (3) filtering off insoluble material.

20. A mineral lubricating oil containing a minor proportion, suflicientto improve the detergent ability of said oil, of a complex metal salt ofa petroleum sulfonic acid produced by the method which comprises thesteps of (1) intimately contacting an oil solution of the sulfonic acidwith an aqueous reagent slurry containing at least about 1.4 equivalentsof calcium hydroxide, at least about 0.3 equivalent of calcium chlorideand at least about 0.3 equivalent of calcium formate, the equivalents ofsaid calcium hydroxide, calcium chloride and calcium formate used beingbased on the total equivalents of acid-hydrogen present in said oilsolution of the sulfonic acid, (2) substantially completely dehydratingthe reaction mixture formed in step 1 and (3) filtering off insolublematerial.

21. A mineral lubricating oil containing a minor proportion, sufficientto improve the detergent ability of said oil, of a complex metal salt ofa petroleum sulfonic acid produced by the method which comprises thesteps of (1) intimately contacting an oil solution of the sulfonic acidwith an aqueous reagent slurry containing at least about 1.7 equivalentsof magnesium hydroxide, at least about 0.3 equivalent of magnesiumchloride and at least about 0.3 equivalent of acetic acid, theequivalents of said magnesium hydroxide, magnesium chloride and aceticacid used being based on the total equivalents of acid-hydrogen presentin said oil solution of the sulfonic acid, (2) substantially completelydehydrating the reaction mixture formed in step 1 and (3) filtering offinsoluble material.

22. A mineral lubricating oil containing a minor proportion, sufiicientto improve the detergent ability of said oil, of a complex metal salt ofa petroleum sulfonic acid produced by the method which comprises thesteps of (1) intimately contacting an oil solution of the sulfonic acidwith an aqueous reagent slurry containing at least about 1.7 equivalentsof barium hydroxide, at least about 0.3 equivalent of barium chlorideand at least about 0.3 equivalent of acetic acid, the equivalents ofsaid barium hydroxide, barium chloride and acetic acid used being basedon the total equivalents of acid-hydrogen present in said oil solutionof the sulfonic acid, (2) substantially completely dehydrating thereaction mixture formed in step 1 and (3) filtering off insolublematerial.

References Cited in the file of this patent UNITED STATES PATENTS Re.23,082 Zimmer Jan. 25, 1949 2,467,176 Zimmer Apr. 12, 1949 2,553,422OHalloran May 15, 1951 30 2,585,520 Van Ess Feb. 12, 1952

1. A COMPLEX METAL SALT OF A HYDROCARBON-SOLUBLE SULFONIC ACID PRODUCEDBY THE METHOD WHICH COMPRISES THE STEPS OF: (1) FORMING A MIXTURE OF AHYDROCARBON SOLUTION OF THE SULFONIC ACID WITH WATER AND A REAGENTCOMBINATION WHICH WILL PROVIDE IN SAID MIXTURE AT LEAST ABOUT 1.4EQUIVALENTS OF METAL HYDROXIDE, AT LEAST ABOUT 0.3 EQUIVALENT OF METALCHLORIDE AND AT LEAST ABOUT 0.3 EQUIVALENT OF AN ALIPHATIC METALCARBOXYLATE HAVING FROM 1 TO 20 CARBON ATOMS IN THE ALIPHATIC PORTIONTHEREOF; THE EQUIVALENTS OF SAID METAL HYDROXIDE, METAL CHLORIDE ANDMETAL CARBOXYLATE BEING BASED ON THE TOTAL EQUIVALENTS OF ACID-HYDROGENPRESENT IN THE HYDROCARBON SOLUTION OLF THE SULFONIC ACID AND THE METALCONSTITUENT OF SAID METAL HYDROXIDE, METAL CHLORIDE AND METALCARBOXYLATE BEING A METAL SELECTED FROM GROUPS I AND II OF THE PERIODICTABLE OF THE ELEMENTS, (2) SUBSTANTIALLY COMPLETELY DEHYDRATING THEREACTION MIXTURE FORMED IN STEP 1 AND (3) FILTERING OFF INSOLUBLEMATERIAL.